Vulcanizing natural or synthetic rubber with a diurethane decomposable to diisocyanate

ABSTRACT

The invention provides a method of vulcanizing a natural or unsaturated synthetic rubber by means of a compound having the general formula:

United States Patent Baker et al.

VULCANIZING NATURAL OR SYNTHETIC RUBBER WITH A DIURETHANE DECOMPOSABLE TO DIISOCYANATE Inventors: Crispin Stuart Leworth Baker,

Stapleford; Douglas Barnard, Welwyn; Maurice Read Porter, Aston, all of England Assignee: The Malaysian Rubber Producers Research Association Filed: Apr. 5, 1974 App]. No.: 458,450

Related US. Application Data Continuation-impart of Set. Nov 172,589, Aug. 17, 19711 Foreign Application Priority Data Aug, 18, 1970 United Kingdom 39804/70 11.8. C1 ..260/77.5 CR; 260/775 TB; 260/795 A; 260/795 B; 260/795 P; 260/833; 260/85.1; 260/923;

260/775 Int. Cl... C08g 53/00; C08g 22/16; COSg 22/32 Field of Search ..260/391, 393,

260/396 N, 390, 77.5 CR, 77.5 AC

OTHER PUBLICATIONS Migrdichian, Org. Syn. V. 1 (1957), P- 448449.

Primary Examiner-H. S. Cookeram Attorney, Agent, or Firm-Wenderoth, Lind & Ponack [57] ABSTRACT The invention provides a method of vulcanizing a natural or unsaturated synthetic rubber by means of a compound having the general formula:

where Q is an aromatic group in the quinonoid form,

R is an aromatic or saturated aliphatic group having a functionality of (m n p),

Y is an organic group joined to (.NHACO.) through oxygen or nitrogen.

8 Claims, No Drawings VULCANIZING NATURAL OR SYNTHETIC RUBBER WITH A DIURETHANE DECOMPOSABLE TO DIISOCYANATE This application is a continuation-in-part of our U.S. Ser. No. 172,589 filed on Aug. 17, 1971. The said application Ser. No. 172,589 relates to certain urethanes having utility as rubber additives.

The present application relates to methods of vulcanizing rubber using urethanes of the same general kind.

U.S. Pat. No. 3,645,980 Ser. No. 862,507) relates to a method of cross-linking a natural or synthetic rubber, which method comprises reacting the rubber with an aromatic nitrosmcompound, e.g. 4-nitrosophenol, and reacting pendent amino or hydroxyl groups in the resulting product with a polyfunctional linking agent, particularly a dior polyisocyanate, so as to cross-link the rubber.

According to a preferred aspect of the said Patent, the aromatic nitroso-compound and linking compound are added to the rubber in the form of a pre-reaction product of a nitrosophenol with a dior polyisocyanate. The pre-reaction product is formed by a reaction between the isocyanate and the nitrosophenol in its oxime form, which may be exemplified as:

RNHCOON=Q=O where R is an organic difunctional group, Ar is an aromatic group and O is the aromatic group in its quinonoid form. This diurethane is believed to subsequently decompose at an elevated temperature to give the nitrosophenol and the di-isocyanate which then vlucanize the rubber.

The use of a pre-reaction product of this type provides equal numbers of nitrosophenol molecules and isocyanate groups in the rubber mix. in fact, it has been found desirable to add an excess of di-isocyanate to increase the cross-linking efficiency of the system. Thus, U.S. Pat. No. 3,645,980 contemplates the use of from 2 to ID pphr of diurethane and up to 6 pphr of an excess of di-isocyanate.

It is a disadvantage of this prior system that many of the available di-isocyanates are toxic and could not readily be handled in the free state by the rubber industry. In one aspect, the present invention seeks to avoid this disadvantage by the use of urethanes which are capable of decomposing to give more isocyanate groups than nitrosophenol molecules.

Accordingly, this invention provides a method of vulcanizing a natural or synthetic rubber having an unsaturated carbon chain, which method comprises heating at from 100C to 200C for 6 hours to 10 seconds a mixture of the rubber with from I to pphr of a compound having the general formula:

where m B l, preferably 1 or 2,

n s: 0, preferably 0, l or 2,

p a 0, preferably 0, 1 or 2,

(n +p) s l, preferably 1 or 2,

Q is an aromatic group in the quinonoid form,

R is an aromatic or saturated aliphatic group having a functionality of (m n p), and

Y is an organic group joined to (.NH.CO) through oxygen or nitrogen, preferably derived from an aliphatic hydroxyl, aromatic hydroxyl, amine, amide, lactam or aliphatic oxime group.

These urethanes may conveniently be prepared from dior polyisocyanates having the formula R(-NCO)IH+II+II' The nature of the dior poly-functional group R is not critical to this invention, and it will be noted that the group R is not altered during the preparation or reaction of the compounds of this invention. Any dior polyisocyanate may be used for this purpose. Examples of di-isocyanates which have been used are:

toluene-2,4-di-isocyanate,

4,4'-di-isocyanato-dicyclohexylmethane, methylene-bis-(4-phenylene-isocyanate), 2,2,4-trimethyl-hexamethylene-l ,6-di-isocyanate, naphthylenel ,S-diisocyanate, and

3,3 ,5 ,5-tetramethylcyclohexyl-l ,7-di-isocyanate.

Other di-isocyanates which may conveniently be used include:

toluene-2,6-di-isocyanate,

hexylene-l ,6-di-isocyanate,

3,3-dimethyl-diphenyl-4,4'-di-isocyanate.

An example ofa tri-isocyanate is sold by Farbenfabriken Bayer under the Trade Mark Desmodur R, which 4,4, 4'-triphenylmethane-triisocyanate.

In addition to di-, tri-, and higher poly-isocyanates, there are available mixtures having a non-integral average number of isocyanate groups per molecule, for example polymethylene polyphenyl isocyanate (PAPl) in the form of a mixture having an average functionality of between 2 and 3. Such mixtures are also suitable starting materials for the preparation of these compounds.

The group (.NH.C0.0.N. Q 0) may be formed by the reaction of an isocyanate group with a nitrosophenol, as explained above and as more fully described in U.S. Pat. No. 3,645,980. The nitrosophenol is one having a nitroso group attached to a carbon atom of an aromatic ring, particularly a benzene or naphthalene ring, and also having at least one hydroxyl group, such that the compound is capable of reaction in its oxime form with isocyanate. The aromatic ring may carry one or more alkyl groups, each containing up to four carbon atoms, provided that such substituents are not so large or so positioned as to prevent the functional group or groups from reacting with the isocyanate. We prefer to use 3-methyl-4-nitrosophenol.

The group (.NH.CO.Y) may be formed by the reaction of an isocyanate group with a compound containing a reactive hydrogen atom provided by, for example, a hydroxyl group or a primary or secondary amino group. Examples of compounds containing a hydroxyl group are alcohols, for example ethyl alcohol; phenols, for example, phenol, thymol, alpha-naphthol; and oximes, for example acetoneoxime, acetophenoneoxime, benzaldoxime. Examples of compounds containing a primary or secondary amino group are amines, for example n-propylamine, phenylbetanaphthylamine; and amides, for example acetamide, benzamide, caprolactam. The reaction is of a kind which is well known, and may be represented thus:

where R is as defined above and X and X' are organic groups (or hydrogen in the case of X) whose natures are unimportant provided that they do not inhibit the reaction. Alternatively, the starting compound of which X and X form a part may be dior polyfunctional with respect to isocyanate, for example resorcinol, bisphenol A, decamethylenediamine.

In the above reaction schemes, X may be monovalent, preferably:

a. a saturated aliphatic group of up to 10 carbon atoms, or

b. an aryl-substituted saturated aliphatic group of up to carbon atoms, or

c. a saturated cycloaliphatic group of up to carbon atoms, or

d. a benzene or naphthalene or pyridine ring, either unsubstituted or substituted by aromatic or satu rated aliphatic groups totalling up to 10 carbon atoms. Also in the above reaction schemes X may be monovalent, preferably hydrogen or one of the groups described by (a) to (d) above. Alternatively, X and X together with the atom or atoms to which they are attached may form a saturated ring system. X may also be dior poly-valent, when it is preferably either a saturated aliphatic group of up to 10 carbon atoms, or a benzene ring or group of benzene rings linked, directly or by aliphatic groups and either unsubstituted or substituted by one or more aromatic or saturated aliphatic groups which contain up to a total of 10 carbon atoms. When X is dior poly-valent, X is preferably a hydrogen atom. The inert residue of the compound containing a reactive hydrogen atom which reacts with isocyanate to form the group (.NHCOY), is not critical to the present invention.

There follows a discussion of the preparation of examples of various classes of compounds within the broad definition set out above.

A. m s l, n 1, p 0. This class is exemplified by the isocyanatourethane formed from a di-isocyanate and a nitrosophenol OCN R NCO OCN R NH.C0.0.N. C H =0 There is always the danger in this reaction of forming unwanted diurethane. For this reason it is preferable to employ at least two moles of di-isocyanate per mole of nitrosophenol, and to carry out the reaction at a temperature below that at which reversible thermal dissociation of the urethane becomes rapid. Thus, we prefer to carry out the reaction at temperatures below 120C, preferably below 100C, when using aliphatic diisocyanates, and below 100C, preferably below 80C, when using the more active aromatic di-isocyanates.

Our preferred procedure is to dissolve the isocyanate in an inert organic solvent in which the urethane is insoluble, e.g. toluene, and to add the nitrosophenol to this solution. The nitrosophenol dissolves slowly, and the urethane comes out of solution as it is formed. It will be appreciated that the proportion of isocyanate to nitrosophenol in solution at any given moment is very high, so that there is little danger of diurethane formation. After removal of the urethane by filtration, we have found that the isocyanate solution can readily be recycled for repeated re-use.

B. m l, n 0, p s 1, Y is the phenoxy group of a monohydric phenol.

These are products which may be formed by reacting a dior poly-isocyanate with a phenol and with a nitrosophenol. The two reactions may be performed in either order, provided that:

a. the first reaction leaves at least one isocyanate group free per molecule, and

b the second reaction is performed under conditions which do not give rise to rapid reversible decomposition of the intermediate reaction product.

The reaction may be exemplified using TDl, phenol and nitrosophenol thus:

The reaction of phenol with isocyanate may be catalysed, e.g. with triethylenediamine. In the absence of a catalyst, this reaction requires temperatures of the order of C, so that we would then prefer to treat TDl with phenol first, and the resulting product with nitrosophenol.

C. m l, n 0, p B 1, Y is the bis-phenoxy grouping of a dihydric or bis-phenol.

The formula of representative compounds in this class may be given as lz where Q, R and X are as previously defined. They may be formed from the reaction of a di or poly-isocyanate with a nitrosophenol and a dihydric phenol or bisphenol. As with compounds of class B, the two reactions of the isocyanate may be performed in either order.

D. m l, n 0, p s 1, Y is a secondary or tertiary amino group.

Compounds of this class are preferably prepared by reacting an isocyanatourethane of class A in a suitable solvent with an equivalent amount of a primary or secondary amine.

E. m l, n 0, p 3 1, Y is the secondary amine grouping of a polymethylenediamine. The formula of representative compounds in this class may be given as NH-(CH -NHCONHRNH- CO O N Q 0 where x is 2 to 10 or more.

Compounds in this class may be prepared by reacting an isocyanatourethane with an aliphatic diamine having the desired chain length.

F. m= l, n=0,p s 1,Y isthe iminoxy groupofan aldoxime or ketoxime. Compounds of this class are preferably prepared by first reacting an excess of a dior polyisocyanate with an oxime and then treating the adduct in a suitable solvent with a nitrosophenol.

G. m =1, 11 =0,p s 1, Y is an amido group. Compounds of this class are preferably prepared by first reacting an excess of a dior polyisocyanate with an amide and then treating the adduct in a suitable solvent with a nitrosophenol.

The vulcanization and other conditions may conveniently be as described in US. Pat. No. 3,645,890. In order to avoid porosity in the vulcanizate and loss of isocyanate, it may be desirable but not essential to add to the rubber mix a drying agent of such a nature and in such an amount as to remove the water by reacting chemically with it. Calcium oxide is an example of such a drying agent, and a suspension of calcium oxide in oil sold under the Trade Mark Caloxol is particularly suitable.

Thorough mixing of the compound with the rubber is necessary, and this may conveniently be achieved by using an open mill or an internal mixer. Generally, an open mill is preferable except when the free isocyanate groups of the compound are blocked as in classes B, C, D, E, F and G above. This cross-linking system may be used either alone, or in conjunction with other systems, e.g. using sulphur, in order to vulcanize the rubber provided that the other vulcanizing ingredients do not interfere with the action of the compounds of this invention. The compounds of this invention may be added to the rubber before, together with, or after such other fillers, additives, or other compounding ingredients as may be determined for the subsequent application of the vulcanizate by the usual practice of the art.

The amount of the compound of this invention to be added to the rubber will depend upon the degree of cure required and can quite readily be determined by methods known in the art. Thus the proportion of the compound may be from 1 to 20, preferably from 5 to 15, parts by weight per hundred parts of dry rubber.

A most important advantage of the system over sulphur systems is that vulcanizates prepared according to it are virtually reversion-resistant. Conditions of cure are therefore not critical, provided always that the temperature of cure is sufficient to form in situ the nitroso compound and the dior poly-isocyanate. Curing conditions may, for example, range from 100C. to 200C, for from 6 hours to 10 seconds, e.g. from 1 hour to 10 minutes.

The cross-linking efficiency of the system may be significantly improved by the addition of certain metal salts of thiols. Examples of such salts include zinc, cadmium and stannous dithiocarbamates, particularly dialkyldithiocarbamates, dithiophosphates, particularly dialkyldithiophosphates, and zinc benzothiazole thiolate. It is to be expected that salts of other thiols and thio-acids, in which the (divalent) metal atom is directly bonded to sulphur, will also be effective. Among the salts, the preferred ones are zinc dimethyl, diethyland di-n-butyl-dithiocarbamates on account of their ready availability.

The amount of the metal thio salt used is not critical, and may suitably be from 0.5 to 10, preferably 1 to 6, parts by weight per hundred parts of dry rubber. Generally, 2 parts of the salt are sufficient to give the desired efficiency increase, and there is little to be gained by going above this figure.

We believe that the heat supplied to vulcanize the rubber causes the compound of this invention to be split into its component parts, which then react with and cross-link the rubber. Thus, isocyanatourethanes (when p 0 as described in class A above) are believed to yield the free nitrosophenol and dior poly-isocyanate; the nitrosophenol reacts with the rubber molecule forming pendent aminophenol groups, and the cross-links are completed by the poly-functional isocyanate molecules.

When the free isocyanate groups of the compounds of this invention are blocked, e.g. with phenols (i.e., when n 0 andp s l as described in classes B, C, D,

E, F and G above), the poly-functional isocyanate is not available to complete the cross-links until the bond with, e.g. the phenol, has been broken. The decomposition generally takes place at a higher temperature than the decomposition of the isocyanate-nitrosophenol bond, and thus reduces the risk of scorch.

Thus, a considerable degree of control over the rate and efficiency of vulcanization obtainable with a particular compound can be obtained by appropriate selection of the nitrosophenol and of the isocyanate, and by blocking free isocyanate groups with an appropriate phenol, alcohol, amine, oxime or amide. For reasons of economy and of rate and efficiency of vulcanization, we prefer to prepare compounds from 3-methyl-4- nitrosphenol and either toluene-2,4-di-isocyanate or methylene-bis-(4-phenylene-isocyanate), and to block free isocyanate groups with phenol or naphthol.

The following Examples illustrate the invention. In the Examples, the following abbreviations are used.

TDl is toluene-2,4-di-isocyanate MD] is methylene-bis-(4-phenylene-isocyanate) Hylene W is 4,4'-di-isocyanato-dicyclohexylmethane Desmodur R is 4,4',4"-tripheny|methanetriisocyanate Bisphenol A is 2,2-di-(4-hydroxyphenyl)-propane SMR is Standard Malaysian Rubber l-lAF is high abrasion furnace Dutrex R is the Trade Name of a rubber processing oil Caloxol C31 is the Trade Name of calcium oxide suspended in oil ZDMC is zinc dimethyldithiocarbamate BR is butadiene rubber (e.g. sold under the Trade Names Cis-4 and lntene 55) SBR is styrene-butadiene rubber (e.g. sold under the Trade Name lntol 1500) NBR is acrylonitrile-butadiene rubber (e.g. sold under the Trade Name Krynac 803) CR is chloroprene rubber (e.g. sold under the Trade Name Neoprene WRT) IR is isoprene rubber (e.g. sold under the Trade Name Natsyn) Examples 1 and 2 illustrate the preparation of typical isocyanatourethanes carrying unblocked isocyanate groups.

EXAMPLE 1 Preparation of isocyanatourethane from 4- nitrosophenol and TDl 4-Nitrosophenol (49.2 g) was stirred with a solution of TD] (348g) in toluene (1200 ml) at room tempera ture for 2 hours under nitrogen. During this time the 4-nitrosophenol dissolved and a bright yellow precipitate formed. The precipitate was filtered off and washed with light petroleum (b.p. 4060C.) to give, after pumping free of solvent, the product, 109g (92%), mp. l38.5- C. (with decomposition). lnfrared absorption bands at 2,280 (NCO), 1,785 (oxime carbamate C=O), and 1,643 cm (quinone C=O).

Analysis C ,,H N;,() requires C, 60.6;

found C, 60.9;

EXAMPLE 2 Preparation of isocyanatourethane from 4- nitrosophenol and MDl Example 15 illustrates the preparation of a typical isocyanatourethane in which the free isocyanate groups are blocked by phenol.

EXAMPLE l5 4-Nitrosophen0 g and MD] g-) were 5 lourless crystals of the product were formed (113 g, Stirred in tolue at for minutes 85%). The mother liquor may be used for further reacunder nitrogen. A yellow precipitate began to form altions. The colourless crystalline product may be recrysmost immediately. The precipitate was filtered off and tallized from a 1:1 mixture of benzene and light petrowashed with toluene and light petroleum (b.p. leum (b.p. 60-80C.) and is believed to be the mono- -60C.) to give, after pumping free of solvent, the 10 adduct (of which there are two possible isomers) of product, 14.6 g (78%), mp. 116-118C. phenol and T01.

Analysis C ll l l O requires (.6151 H. 4.1 N. 11.2

found C, 67.3; H. 4.2 N, 10.8%

Examples 3 to 14 relate to the preparation of other This mono-adduct (165 g, 0.62 mole) and 4- unblocked isocyanatourethanes by methods similar to nitrosophenol (72 g, 0.59 mole) were stirred in toluene those used in Examples 1 and 2. Details are given in (2 l) for minutes at C. during which time a dense Table 1. yellow precipitate had formed. This was filtered off and TABLE 1 ISOCYANATOURETHANES Example Nitrosophcnol mole Diisocyanatc Mole Solvent Temp. Time. Yield mp.

C min. C.

1 4-nitrosophenol 1 TD] 5 Toluene RT 120 92 139-145 3 1 MD! 5 7o 30 78 116-118 3 1 Hylcne W 5 60 20 -87 4 1 Desmodur R 3 Dichloro- RT 180 94 80-82 methane 5 3-mcthyl-4-nitrosophcnol 1 "rm 5 Toluene RT 150 192 194 6 Lmethyl-4-nitrosophenol 1 MD] 5 RT 95 -152 7 2 methyl-4-nitrosophcnol 1 TD] 5 RT 240 71 1 17-1 19 8 5mcthyl-2'isupropyl-4-nitrosophenol 1 TDI 5 RT 60 94 15 5-157 9 Z-mcthyl-S-isopropyl-4nitrosophenol 1 TDI 5 RT 240 84 129-131 10 3'isopropyl-4-nitrosophcnol 1 TD] 5 RT 40 61 122-123 1 1 3.5-dirncthyl 4-nitrosophcnol 1 TDI 5 RT 73 171-173 12 2 ,(i'dimethyl-4-nitrosophenol 1 TD] 5 RT 120 43 134-136 13 2.fi diisopropyli-nitrosophcnol 1 TDI 5 RT 180 42 103-105 14 Lnitro-Z-naphthol l TDl 5 RT 90 61 151.5

*Triethylendiamine catalyst employed.

washed with toluene. Yield of mixed adduct: 217 g (94%), mp. 189C. Infrared absorption bands at 1,760 (oxime carbamate C=O), 1,747 (urethane C=O), 1,650 cm (quinone C=0).

Other phenol-blocked isocyanatourethanes were made similarly. Details are given in Table ll. In all cases, equimolar proportions of the nitrosophenol and the mono-adduct of phenol and TDl described in Example 15 were reacted together in toluene.

Example was repeated using 3-methyl-4- nitrosophenol in place of 4-nitrosphenol and using various blocking compounds. The results are given in Table 111.

TABLE Ill Blocked Compounds Example Blocking Compound Temp. Time Yield m.p.

C. (min.) 9% C.

21 phenol 65 90 92 195 197 22 thymol 70-80 360 55 156 23 Z-naphthol 60-70 120 90 I78 24 ethanol 70-80 78 156 EXAMPLE 25 after filtration, was pumped free of solvent to yield 4.08

n-Propylamine (1.77 g., 0.03 mole) in dichloromethane (100 ml.) was added dropwise over 0.5 hour at room temperature to the isocyanatourethane of Example l (8.91 g, 0.03 mole) in dichloromethane (100 ml.). The red precipitate formed was filtered off, washed with dichloromethane and pumped free of solvent to give 8.1 g. (76%) of product, m.p. 150l60C.

Examples 26 to 28 relate to the preparation of blocked isocyanatourethanes using difunctional blocking agents.

EXAMPLE 26 Bis-phenol A (1.14 g, 0.005 mole) and TD] (17.4 g, 0.1 mole) were warmed with stirring to 40C. for 2 hours in toluene (20 ml) and in the presence of triethylenediamine (0.02 g, 4 mole with respect to bisphenol A) as catalyst. On cooling, the product was precipitated by addition of light petroleum (b.p. 6080C.). The white coarse powder obtained, believed to be mainly the bis TDl adduct of bis-phenol A, was purified by prolonged extraction with light petrog (99.4%) of the product obtained in Example 26, m.p. 108-1 15C.

EXAMPLE 28 Decamethylenediamine (2.58 g, 0.015 mole) in dichloromethane (100 ml) was added slowly over a period of 20 minutes to a stirred suspension of the isocyanatourethane of Example 1 (8.91 g, 0.03 mole) in dichloromethane (200 ml). After addition the reaction mixture was warmed to C for 15 minutes. On cooling the product was filtered off and, after washing 3 times with dichloromethane, was pumped free of solvent. Yield, 9.6 g (84%).

EXAMPLE 29 Acetoneoxime (7.3 g, 0.1 mole) in dry toluene (40 ml) was added dropwise to a well-stirred solution of TD] (34.8 g, 0.2 mole) in toluene (100 ml). The temperature of the mixture rose about 10 during the course of the addition and on cooling to room temperature a colourless crystalline solid, m.p. l10-l 12C, was obtained in 49% yield.

H, 5.3. N. 170 found C. 58.5; H, 5.3- N. 17.5%

leum (b.p. 6080"C.). The product (0.576 g) was stirred with chloroform (25 ml) and the insoluble material filtered off. To the filtrate was added 4- nitrosophenol (0.18 g, 0.00146 mole) and the mixture refluxed for 1 hour with stirring. The resulting yellow chloroform solution was decanted into light petroleum (b.p. 40-60C.) to precipitate a yellow solid which, after filtering, was pumped free of solvent. The product, 0.4 g. (67%), m.p. 108l15C. is believed to possess the structure and showed infrared absorption bands at 1,745 (oxime carbamate C=O), 1,730 (urethane C=O), and 1,650 cm (quinone C=O).

sis, 100%.

Other oxime-blocked isocyanatourethanes were made similarly. Details are given in Table IV.

EXAMPLE 30 Acetamide (11.8 g, 0.2 mole) and TDl (69.6 g, 0.4

Analysis C., ,H;.,,N,;O requires C. 65.7; H, 4.7; N, 10.2

found (1.656; H, 5.0; N, .9

EXAMPLE 27 The isocyanatourethane of Example 1 (2.97 g, 0.01 mole) and bisphenol A (1.14 g, 0.005 mole) were warmed with stirring to 40C. for 1 hour in chloroform (25 ml) and in the presence of triethylenediamine (0.03 g, 5 mole with respect to bis-phenol A) as catamole) were heated under reflux in dry toluene (300 ml) for 18 hours with continuous stirring. The solid obtained in 55% yield on cooling continued of the theoretical number of isocyanate groups for a 1:1 adduct by titration with di-nlbutylamine in dimethyl sulphoxide. Work-up of the mother liquors provided a further 41% yield. Recrystallization from a toluenepetroleum mixture gave the adduct, m.p. l489C. isocyanate groups, 100% of theoretical.

EXAMPLE 32 The above standard rubber formulation was vulca- Analysis: C H N O requires C. 56.65; found C. 57.8;

Other adducts were prepared similarly and are described in Table l\/.

The acetamide adduct g, 0.02 mole) and 4- nitroso-3-methylphenol (2.9 g. 0.2 mole) were heated in dry toluene (100 ml) with stirring for 1.5 hours at 70C. The copious yellow precipitate obtained on cooling was washed successively with pentane and acetone and dried under vacuum. Yield 91%. Total nitrosophenol analysis, 97%.

Other amide-blocked isocyanatourethanes made similarly. Details are given in Table IV.

The urethanes of Examples 1 to were used as vulwere Table IV Blocking Agent Oximcor Amide TDl Monoadduct Oxime or Amidcblockcd isocyanutourcthane from TD] and 4-nitroso- 3-mcthylphcnol Combined nitr0su Yicld M.p. Found In Rcquircd (72 NCO Yield (94) phenol 1 1C) Groups (7% of (7t of theory) C H N C H N theory! Acetoneoximc 49 110-2 58.5 5.3 17.5 58.3 5.3 17.0 99 88 I00 Acctophcnoncoxime oil 656 4.7 13.8 66.0 4.9 13.6 99 99 97 Cyclohcxunoncuximc 73 95 8 62.8 6.1 15.2 62.7 6.0 14.6 104 99 100 Propionaldoximc 60 oil 593 5.5 17.4 58.3 4.9 17.1 95 95 99 Benzaldoxime 108-l 12 65.6 4.5 14.5 65.1 4.4 14.2 102 99 93 Acctumidc 96 1411-9 57.8 4.11 17.9 56.6 4.8 121.0 100 91 97 Prupionamidc 100 146-7 586 5.3 17.3 58.3 5.3 17.0 100 96 96 Luuramidc 100 66-73 67.0 8.6 11.5 67.5 8.4 11.3 102 92 Stcuramidc 70 68-74 68.9 9.2 9.8 70.8 9.5 9.2 102 77 93 Acrylamidc 86 176-7 59.7 4.5 17.5 58.7 4.5 17.1 99 94 91 Nicotinamidc 93 220-240 98 80 Bcnzamidc 9U 65.1 4.1 14.3 65.1 4.4 14.2 98 80 Caprolactum 011 62.3 5.8 14.7 62.5 5.9 14.6 98 95 101 canizing agents in various gum and filled natural and TABLE V synthetic rubber formulations. For Examples 31 and 32. the following standard black-filled natural rubber lsocyanatourethane f C n ntration MR l 0(MN1m*) formulation was used. 50 Example pphr of Vulcanizate 1 8 2.54 Natural rubber (SMR 51 5 9 HAF black 50 7 9 Dulm R 4 10 9.11 1.41 Caloxol C31 5 11 914 C 2 55 12 9.4 2.20 Vulcanizing agent varies l L0 L71 [5 10.5 3.12 16 1 1.7 2.33 EXAMPLE 3] 17 11.7 2.54 19 13.7 1.34 The above standard standard formulation was used 20 12.9 1.92 7 with 8 pphr of the isocyanatourethane of Example 1, 6O 3: and was cured at C for 20 minutes. The initial 23 13.1 1.00 properties of the vulcanizate were as follows: 24

Hardness. BS 68 Relaxed Modulus. MR 100, MN/m 2.54 Tensile Strength, MN/m" 26.2 65 EXAMPLE 3?) Elon ation at break, 71 415 Tcurgsmngth [may N/mm 17.6 The isocyanatourethanes of Examples 1 and 2 were Dunlop Resilience. 7311 used to prepare natural rubber gum vulcanizates,

whose tensile properties are reported in Tables VI and VII below.

Table VI NR gum vulcanizates cured with product of Example 1 Compound Ingredients SMR 5 I I00 I00 I00 I00 I00 I00 I00 Caloxol (3| 5 5 5 5 5 5 5 ZDMC 2 2 2 2 2 2 2 2 Product of Example I 3 4 5 6 7 8 '9 l0 Cure. min. at 140C, l 20 20 2O 20 20 20 Initial vulcanizate properties Relaxed modulus. MR I00. MN/m" 0.50 (lhl 0.71 0.8] 0.90 L04 l.l2 I23 Tensile Strength. MN/m 20.8 20.5 [8.4 23.6 2|.7 26.5 28.3 2L6 Elongation at break. l 792 689 589 654 532 570 563 494 Table VII NR gum vuleanizales cured with product of Example 2 Compounding Ingredients SMR 5 I00 I00 I00 I00 I00 I00 I00 I00 Caloxol C3l 5 5 5 5 5 5 5 5 ZDMC 2 2 2 2 2 2 2 2 Product of Example 2 2 3 4 5 6 7 8 9 Cure, min at 150C 40 40 4O 40 40 40 40 40 Initial vulcanizatc properties Relaxed modulus. MR I00. MN/m 0.35 0.45 0.56 0.64 0.76 0.85 096 l.0l Tensile Strength. MNl/m 9.3 [4.4 I96 20.1 16.0 20.] 22.8 [7.9 Elongation at break "l: 784 8l3 778 721 62) 634 620 548 34 3O EXAMPLE Table 1x This Example demonstrates the ability of the compounds of this invention to vulcanize synthetic rubbers p d having unsaturated carbon-chains. Formulations are Of Conccmrfllm" Mooney Scorch I 35 Example (pphr) (t 51min. (t 35im1n. given in Table VIII below. In all cases, the VUICHI'IlZlDg agent was the unblocked isocyanatourethane from 14 6 4,5 3-methyl-4-nitrosophenol and TDI. Mooney Scorch (at 3: 5 1 5) l0 pphr ofvulcanizing agent) and Relaxed Modulus (at 5 3 varying proportions of vulcanizing agent) are also given in the Table. In considering the scorch times, it should 40 be borne in mind that curin with these isoc anatoure' g y EXAMPLE 36 thanes takes place progressively over a period of time, in contrast to the sudden delayed action curing which is typical of sulphur systems. The vulcanization conditions were 2 hours at 150C, except for CR (6 hours at l50C.).

TABLE VIII SYNTHETIC RUBBERS MOONEY SCORCH MODULUS Isocyanato Ioscyanato- MR IO(] Rubber HAF Dutrcx Caloxol C3l ZDMC urethane (t+5) 120C. urethane MN/m" black R pphr min. pphr (Sis-4 I00 4 S 2 l0 5 6 1.99 BR Intcne I00 50 4 S 2 l0 7 6 1.77 SBR Intol I500 100 S0 4 5 2 I0 I25 10 l.fi| NBR Krynae 803 I00 50 4 5 2 l0 ll.5 15 1.38 CR Neoprene WR'I I00 50 4 None 2 l0 Immediate 9 4.87 IR Natsyn I00 50 4 5 2 10 I5 I0 [.37

EXAMPLE 35 when mixes were heated in the Monsanto Rheometer This Example demonstrates the vulcanizing ability of the compounds of certain Examples by reference to the Mooney Scorch times in a standard unfilled natural rubber formulation containing Caloxol C31 (5 pphr) (ASTM D2084-7I The formulation used was that in Examples 31 and 32, the vuleanizing agent being the isocyanatourethane derived from 3-methyl-4 nitrosophenol and TDI blocked by various blocking agents. The quantity of vulcanizing agent used was in l5 16 each case the molar equivalent of 12 pphr of the same We claim: isocyanatourethane blocked with phenol. 1. A method of vulcanizing a natural or synthetic rub- TABLE X her having an unsaturated carbon chain which method comprises heating at from 100C to 200C for from 6 ixtu f ru b r w' f Block-mg Mooney Scorch Monsanto Rhcometer 5 hours to Seconds a m m 0 the b 8 1th Tom Agent in 120C at 1 0 l to 20 pphr ofa compound having the general formula 1 1M!!! (MIFMLI (MHR'MLY MI.) lhi'jn,

Phenol 22 l Acetamide 16 l 86 1O R(.NH.C0.0.N=Q=O),,, (.NCO), (.NHCOY) Propionamide 14 86 Lau ramide I0 44 I Stearamide I0 44 Acrylamide I8 I 14 Nicotinamide I5 86 Benzamidc 22 I55 15 Caprolactam 12 99 where Acetoneoxime 4 110 m 3 1 Aceto- 8 I08 0 phenoncoxn ime p 3 0 Cyclohex- 8 70 anoneoximc "i S l iropionaldox- 8 56 Q is an aromatic group In the qulnonoid form, gimmoximc 8 75 R 15 an aromatic or saturated aliphatic group having Quinol I5 124 a functionally of (m n p), and R sur i l 8 83 i g 'g n 84 Y is an organ c group oined to (.NHCO.) through Styrenated 12 92 23 oxygen or nitrogen. 2. A method as claimed in claim 1, wherein in the compound of formula (I) m is l or 2 n is 0, l or 2 M M M and M, being as defined in ASTM D 208471 T.

EXAMPLE 37 p is O, l or 2 and lsocyanatourethanes and phenol-blocked isocyanat- P) is 1 ourethanes were prepared from 3-methyl-4- 3. A method as claimed in claim 1, wherein in the nitrosophenol and various diisocyanates and comcompound of formula (I), Q is a benzene ring in its pounded and vulcanized in the formulation of Examparaquinonoid form or a naphthalene ring system in a ples 31 and 32 The properties recorded for the mixes 35 quinonoid form. and vulcanizates are shown in Table XI. 4. A method as claimed in claim 3, wherein in the TABLE XI compound of formula (I) the group O carries one or more alkyl groups each containing up to four carbon atoms attached to the aromatic ring.

Key: ICTM isocyanato urethane from Hylene TM (Du pontybcheved to an 80:20 wt. per cent mixture 40 5. A method as claimed in claim 1, wherein m the of toluene-2,4- and toluene-2K di-isocyanate.

lClS isocyanatourethane from Desmodur l5 cOmPOund of formula (I) (Bayer), believed to be m 15 l naphthalene-l,5-di-isocyanate n O l PBJCTM phenol-blocked ICTM PBJCEN phenol-blocked isocyanatourethane from P 15 0 1 Suprasec EN (1C1), believed to be an 80:20 wt. i 1 per cent mixture of toluene-2,4- and toluencq 6 di isocyanam Q is a benzene ring in its para-quinonoid form with xulcatnizing ICTM lClS PB-ICTM B C or without a methyl group attached in a position gig g 10 H1 ortho to the adjacent nitrogen atom, (pphr) R 15 toluene-2,4- or methylene-b|s-(4-phenylene-), Mooney Search 95 6 l9 2] and at 120C. It+5)m in, Y 15 OC H or --OC, H gfi fi i 120 50 5O 6. A method as claimed in claim 1, wherein a drying mm agent is included in the rubber mix to remove water by reacting chemically with it. Relaxed mg 133 159 1,54 55 7. A method as claimed in claim 1, wherein a zinc, rhr iirdludgs f cadmium or stannous dithiocarbamate or dithiophos- Tensileiitrength, 22,5 25.9 23,5 225 phate, or zinc benzothiazole thiolate, is included in the SIN/mi 30 4 469 449 rubber mix. 2g 8. Rubber vulcanized by the method in claim 1. 

1. A METHOD OF VULCANIZING A NEUTRAL OR SYNTHETIC RUBBER HAVING AN UNSATURATED CARBON CHAIN WHICH METHOD COMPRISES HEATING AT FROM 100*C TO 200*C FOR FROM 6 HOURS TO 10 SECONDS A MIXTURE OF THE RUBBER WITH FROM 1 TO 20 PPHR OF A COMPOUND HAVING THE GENERAL FORMULA (I)
 2. A method as claimed in claim 1, wherein in the compound of formula (I) m is 1 or 2 n is 0, 1 or 2 p is 0, 1 or 2 and (n + p) is 1 or
 2. 3. A method as claimed in claim 1, wherein in the compound of formula (I), Q is a benzene ring in its paraquinonoid form or a naphthalene ring system in a quinonoid form.
 4. A method as claimed in claim 3, wherein in the compound of formula (I) the group Q carries one or more alkyl groups each containing up to four carbon atoms attached to the aromatic ring.
 5. A method as claimed in claim 1, wherein in the compound of formula (I) m is 1 n is 0 or 1 p is 0 or 1 (n + p) is 1 Q is a benzene ring in its para-quinonoid form with or without a methyl group attached in a position ortho to the adjacent nitrogen atom, R is toluene-2,4- or methylene-bis-(4-phenylene-), and Y is -OC6H5 or -OC10H7
 6. A method as claimed in claim 1, wherein a drying agent is included in the rubber mix to remove water by reacting chemically with it.
 7. A method as claimed in claim 1, wherein a zinc, cadmium or stannous dithiocarbamate or dithiophosphate, or zinc benzothiazole thiolate, is included in the rubber mix.
 8. Rubber vulcanized by the method in claim
 1. 